1. Field of the Invention
The present invention relates to a method of processing of silver halide color photographic materials, particularly a method of processing of silver halide color photographic materials wherein the volume of a replenisher is decreased.
2. Description of the Prior Art
Development processing of silver halide color photographic materials basically consists of two major steps, i.e., color-developing (in the case of color reversal material, black-and-white first development prior to that) and desilvering. Desilvering consists of bleaching and fixing steps, or a monobath bleach-fixing step which may be conducted either together with the former steps or alone. In the case of necessity, additional treatment steps such as water washing, stop treatment, stabilizing treatment and pretreatment for the acceleration of development may further be added.
In color development, exposed silver halide is reduced to silver and, at the same time, oxidized aromatic primary amine developing agents react with couplers to form dyes. During this process, halide ions evolving through dissociation of silver halide are eluted in a developing solution and accumulate therein. Meanwhile, color development agents are exhausted by reaction with the aforesaid couplers. Further, other constituents are taken out by being held in photographic materials and concentrations of the constituents in the developing solution decrease. Accordingly, in a process for the continuous development processing of a large amount of the silver halide photographic materials, for instance, by an auto-developing machine, a means is required to maintain concentrations of constituents of a color-developing solution in a certain range in order to avoid fluctuations of results of finished development due to changes in the concentrations of the constituents.
For instance, constituents to be consumed such as a developing agent and a preservative may be incorporated in a replenisher in high concentration when such a high concentration has little influence. In some cases, the concentrations of eluted materials, such as halogens, which have an effect of suppressing development are set at low levels in a replenisher or such materials are not included. Further, some compounds may be included in a replenisher so as to preclude influences of eluted materials. Alternatively, a pH or concentrations of alkali or chilate agents may be controlled. As a means for the above, it is usual to add a replenisher which supplies short constituents and dilute increasing constituents. A large volume of overflow liquid necessarily occurs as a result of such addition of the replenisher, which causes problems in process economy and environment protection.
The volume of the replenisher for a developing solution is generally 1,100 to 1,300 ml per m.sup.2 of light-sensitive material to be treated, depending somewhat upon which types of light-sensitive materials are to be treated. A smaller amount of the replenisher is more desirable from the above-mentioned viewpoint. However, it becomes difficult to obtain constant results of finished development and, accordingly, it is impossible in practice to decrease the amount of the replenisher below the aforesaid range.
Another reason for the fluctuations of results of finished development is a dense fog caused in a development process of silver halide color photographic materials and a change of a fog during storage of raw light-sensitive materials. Light-sensitive materials having a high foggy property have a tendency of showing a large difference in fog between development conditions where the temperature of a developing solution rises or its pH rises to facilitate lowers to inhibit fogging. As a result, large fluctuations in the results of finished development are often seen. No further explanation is required because light-sensitive materials which have a large change in fog during storage of the raw materials have a tendency of exhibiting large fluctuations in the results of finished development.
Inclusion of various antifoggants in light-sensitive materials is known as a means to prevent fogging in silver halide color photographic materials and to solve the problem of increased fog during storage of the raw materials.
That is, heterocyclic mercapto compounds are known as antifoggants having remarkable effect of inhibition of fogging or suppression of increasing fogging during storage of the raw materials, such as mercapto thiazoles, mercapto benzthiazoles, mercapto benzimidazoles, mercapto thiadiazoles, mercapto tetrazoles, especially 1-phenyl-5-mercapto tetrazole, and mercapto pyrimidines.
It is recognized that the above antifoggants or stabilizers successfully suppress fogging during storage of the raw materials and lower the fluctuations in the results of finished development when normal supply of a replenisher is done. However, if the volume of the replenisher for the developing solution is decreased, such antifoggants or stabilizers included in the light-sensitive materials cause an adverse effect of rather magnifying the fluctuations of results of finished development, and in particular, changes in sensitivity.